CN115557802A - Ceramic membrane and method for producing same - Google Patents
Ceramic membrane and method for producing same Download PDFInfo
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- CN115557802A CN115557802A CN202211082986.2A CN202211082986A CN115557802A CN 115557802 A CN115557802 A CN 115557802A CN 202211082986 A CN202211082986 A CN 202211082986A CN 115557802 A CN115557802 A CN 115557802A
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- 239000012528 membrane Substances 0.000 title claims abstract description 143
- 239000000919 ceramic Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 75
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000009825 accumulation Methods 0.000 claims abstract description 6
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 59
- 238000002791 soaking Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 25
- 235000000346 sugar Nutrition 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 235000014633 carbohydrates Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 150000002772 monosaccharides Chemical group 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 25
- 238000009826 distribution Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 33
- 239000003153 chemical reaction reagent Substances 0.000 description 25
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 21
- 239000008103 glucose Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000003814 drug Substances 0.000 description 11
- 229940079593 drug Drugs 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 229960004853 betadex Drugs 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 229920001503 Glucan Polymers 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007905 drug manufacturing Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a ceramic membrane, which comprises a metal oxide particle accumulation type ceramic membrane main body, wherein a carbon layer is attached to the surface of metal oxide particles, and carbon spheres are arranged in gaps among the metal oxide particles. The method takes the saccharides which are cheap and easy to obtain and have wide sources as raw materials to form the carbon layer on the surface of the metal oxide particles, so that the problem of poor stability in an acid solution is solved, and the carbon spheres in the gaps further optimize the pore size distribution range of the ceramic membrane so as to improve the performance of the ceramic membrane.
Description
Technical Field
The invention belongs to the technical field of ceramic membrane preparation, and particularly relates to an acid-resistant ceramic membrane and a preparation method thereof.
Background
Ceramic membranes are one of inorganic membranes, and have the advantages of high mechanical strength, high temperature resistance, organic solvent resistance, long service life, high treatment capacity and the like, so that the ceramic membranes are widely applied to industries such as wastewater treatment, oil-water separation, food processing and drug manufacturing, metal smelting, textile dyeing and the like, wherein many processes relate to the treatment of acid solutions, such as the recovery of acid-containing wastewater in industrial acid waste extracting solutions and electroplating industries, the treatment of fermented acid wastewater, acid juice purification, drug purification and separation, mining and the like.
The ceramic membrane is a particle-stacked separation membrane prepared by adding additives such as a binder and a sintering aid to metal oxide powder such as alumina, zirconia and titania serving as a raw material by a sol-gel method, a solid particle sintering method, a wet chemical method, a chemical vapor deposition method or an atomic layer deposition technology, and the like, wherein pore channels of the porous separation membrane are gaps formed by stacking metal oxide particles. The metal oxide particles and additives during the preparation process are exposed to a strongly acidic solution or are unstable when operated in an acidic solution for a long time, and the channel microstructure, the properties of the inner walls of the pores and the mechanical properties of the ceramic membrane are damaged accordingly. Therefore, the metal oxide particle-stacking type ceramic membrane has a problem of poor stability in an acidic solution, and this disadvantage greatly limits the use of the ceramic membrane. In addition, narrow pore size distribution is an important condition for such ceramic membranes to have good separation selectivity, however, the size of the voids formed by particle accumulation is not uniform, and the pore size distribution of the ceramic membrane still has room for optimization.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to solve the problems of the prior art by depositing an acid-resistant protective layer on the inner wall surfaces of the ceramic membrane pore channels by adopting a physical or chemical process, filling the larger pore channels in the ceramic membrane and optimizing the pore size distribution, thereby overcoming the defects in the prior art and improving the performance of the porous ceramic membrane from multiple aspects.
In order to achieve the above object, the present invention provides a ceramic membrane comprising a metal oxide particle-stacked ceramic membrane body, an acid-resistant carbon layer attached to the surface of the metal oxide particles, and carbon spheres for adjusting the gap between the metal oxide particles.
The method takes the saccharides which are cheap and easy to obtain and have wide sources as raw materials to form the carbon layer on the surface of the metal oxide particles, solves the problem of poor stability in an acid solution, and further optimizes the pore size distribution range of the ceramic membrane by the carbon spheres in the gaps so as to improve the performance of the ceramic membrane.
Preferably, in the above technical solution, the metal oxide particles are alumina, zirconia, titania or other metal oxides suitable for preparing metal ceramic membrane.
Preferably, in the above aspect, the carbon layer is an encapsulated carbon layer formed on the surface of the metal oxide particle after the sugar substance is carbonized.
In the preparation method of the ceramic membrane, the metal oxide particle accumulation type ceramic membrane main body is placed in a sugar solution to be fully soaked, and the soaked ceramic membrane main body is subjected to hydrothermal reaction to obtain the carbon-coated ceramic membrane.
The hydrothermal reaction process is a generic term for chemical reactions carried out in a fluid such as water, an aqueous solution or steam under a certain temperature and pressure.
Preferably, in the above technical scheme, the sugar solution is a sugar aqueous solution, and the concentration of the sugar solution is not lower than 36g/L.
Preferably, in the above technical solution, the sugar is monosaccharide, disaccharide, polysaccharide or other sugars capable of forming carbon by hydrothermal reaction.
Preferably, in the above technical scheme, the hydrothermal reaction time is not less than 4 hours, and the reaction temperature is not less than 120 ℃.
Preferably, in the above technical solution, the reaction nodes of the hydrothermal reaction are: and (3) changing the ceramic membrane from white to brown or brown-like, and stopping the reaction to obtain the carbon-coated ceramic membrane.
Preferably, in the above technical solution, the ceramic membrane is sufficiently soaked in the sugar solution by soaking or hydraulic pressure.
Preferably, in the above technical solution, the carbon-coated ceramic membrane is a shell structure, and the shell structure is an encapsulated carbon layer formed on the surface of the ceramic membrane substrate particles after the carbohydrates in the sugar solution are carbonized.
Preferably, in the above technical solution, the carbon-coated ceramic membrane is washed with water and ethanol until the eluate is colorless, and then dried. The separation membrane mainly has two functions, one is concentration and the other is impurity removal, and a common membrane for concentration permeates water molecules, so that the concentration of the solution is realized at the feed side, and trapped fluid is finally collected; the membrane for impurity removal needs to prevent impurities from permeating, impurity removal is realized, and finally permeate liquid is collected. Products in the hydrothermal reaction may remain on the membrane pore and the surface of the carbon layer, and if the products are not cleaned, the products will contaminate the membrane permeate.
Compared with the prior art, the invention has the following beneficial effects: compared with the prior art, the method has the following beneficial effects: the method utilizes the aqueous solution of sugar as a raw material to carry out hydrothermal reaction, the sugar biomass generates reactions such as dehydration, degradation, polycondensation, rearrangement and the like during the reaction, in the early stage of the reaction, the generated small molecular substances are firstly combined with the hydroxyl on the surface of metal oxide particles forming a ceramic membrane, the adhesion of the surfaces of the particles is realized, hydrothermal products are continuously complexed, adhered and settled in the subsequent reaction, and finally the surfaces of the accumulated metal oxide particles are coated with a carbon layer to block the contact of acid substances and the metal oxides, and meanwhile, the carboxyl on the surface of the carbon layer further excludes the approach of the acid substances; meanwhile, small molecules generated by dehydration and degradation in the reaction form carbon spheres through processes of polycondensation, nucleation, mutual adhesion and the like, so that gaps formed by the accumulation of metal oxide particles are filled, and the pore size distribution of the ceramic membrane is optimized. The separation pore channel of the carbon-coated ceramic membrane is still based on a gap formed by the accumulation of metal oxide particles, and the pore channel of the separation membrane is modified by the carbon coating and the carbon spheres. The invention is characterized in that: 1. the acid resistance of the ceramic membrane is improved; 2. the pore size distribution of the ceramic membrane is optimized.
Drawings
FIG. 1 shows the appearance of ceramic films before and after carbon coating: (a) (b) (c) are SEM and TEM results of the surface and cross section of the alumina ceramic film, respectively, and (d) (e) (f) are SEM and cross section of the carbon-coated alumina ceramic film, respectively.
Fig. 2 shows pore size distribution curves for ceramic membranes.
Fig. 3 mass loss for alumina ceramic membranes and carbon-coated alumina ceramic membranes.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations such as "comprises" or "comprising", etc., will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
1 test reagent: glucose (analytical grade, chemical reagents of national drug group, ltd);
2, experimental steps:
s1, preparing 36g/L aqueous solution of glucose;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a glucose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 4 hours, stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 2
1 test reagent: glucose (analytical grade, chemical reagents of national drug group, ltd);
2, experimental steps:
s1, preparing 36g/L aqueous solution of glucose;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a glucose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 200 ℃ for 14 hours, and stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 3
1 test reagent: glucose (analytical pure, chemical reagents of the national drug group, ltd);
2, experimental steps:
s1, preparing 90g/L glucose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a glucose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 180 ℃ for 8 hours, stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 4
1 test reagent: glucose (analytical pure, chemical reagents of the national drug group, ltd);
2, experimental steps:
s1, preparing 145g/L glucose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a glucose solution in a soaking or hydraulic mode;
s3, carrying out hydrothermal reaction at 180 ℃ for 8 hours, and stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 5
1, experimental reagent: xylose (Shanghai-derived leaf Biotech Co., ltd.);
2, experimental steps:
s1, preparing 90g/L xylose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a xylose solution by adopting a soaking or hydraulic mode;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, and stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 6
1, experimental reagent: fructose (shanghai-derived leaf biotechnology limited);
2, experimental steps:
s1, preparing 90g/L of fructose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a fructose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 7
1 test reagent: maltose (shanghai source leaf biotechnology limited);
2, experimental steps:
s1, preparing 90g/L maltose water solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a maltose solution in a soaking or hydraulic mode;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 8
1 test reagent: sucrose (analytical pure, chemical reagents of national drug group, ltd);
2, experimental steps:
s1, preparing 90g/L of sucrose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a sucrose solution in a soaking or hydraulic mode;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, and stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 9
1, experimental reagent: beta-cyclodextrin (analytical pure, chemical reagents of national drug group, ltd.);
2, experimental steps:
s1, boiling to prepare 90g/L beta-cyclodextrin water solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a beta-cyclodextrin solution by adopting a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, and stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 10
1, experimental reagent: dextran (nantong femto biotechnology limited);
2, experimental steps:
s1, preparing 90g/L glucan aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in the glucan solution in a soaking or hydraulic mode;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
example 11
1 test reagent: soluble starch (analytical grade, chemical reagents of national drug group, ltd);
2, experimental steps:
s1, boiling to prepare 90g/L starch water solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 100 nm) in a starch solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 160 ℃ for 6 hours, and stopping the reaction to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 12
1 test reagent: glucose (analytical grade, chemical reagents of national drug group, ltd);
2, experimental steps:
s1, preparing 90g/L glucose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 800 nm) in a glucose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 180 ℃ for 8 hours, stopping the reaction, naturally cooling, and taking out to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 13
1, experimental reagent: glucose (analytical grade, chemical reagents of national drug group, ltd);
2, experimental steps:
s1, preparing 90g/L glucose aqueous solution;
s2, fully soaking the alumina ceramic membrane (with the aperture of about 3000 nm) in a glucose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 180 ℃ for 8 hours, stopping the reaction, naturally cooling, and taking out to obtain the carbon-coated alumina ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated alumina ceramic membrane until an eluate is colorless, and drying.
Example 14
1 test reagent: glucose (analytical pure, chemical reagents of the national drug group, ltd);
2, experimental steps:
s1, preparing 90g/L glucose aqueous solution;
s2, fully soaking the zirconium oxide ceramic membrane (with the aperture of about 400 nm) in a glucose solution in a soaking or hydraulic manner;
s3, carrying out hydrothermal reaction at 180 ℃ for 8 hours, stopping the reaction, naturally cooling and taking out to obtain the carbon-coated zirconium oxide ceramic membrane, wherein the surface of the ceramic membrane is changed from white to brown;
and S4, cleaning the carbon-coated zirconia ceramic membrane until an eluate is colorless, and drying.
Comparative example 1: the comparative example provides an alumina ceramic membrane, which is washed by deionized water and dried.
Test example 1
1. Morphology of scanning electron microscope and transmission electron microscope
And respectively observing the appearance of the ceramic membrane by adopting a field emission scanning electron microscope and a transmission electron microscope, spraying gold before the scanning electron microscope sample is used, grinding the transmission electron microscope sample into powder before the transmission electron microscope sample is used, and dispersing the powder in ethanol, thereby performing appearance characterization on the ceramic membrane in the embodiment 3 and the comparative example 1.
2. An experimental instrument: sammerfea QUANTA FEG 250 field emission scanning electron microscope, hitachi H-7800 transmission electron microscope;
3. the experimental results are as follows:
as can be seen from fig. 1, the ceramic membrane particles of the carbon-coated membrane are coated with an obvious carbon layer, and carbon spheres grow at the defect sites to optimize the pore size distribution.
FIG. 1 shows the appearance of ceramic films before and after carbon coating: (a) (b) (c) are SEM and TEM results of the surface and cross section of the alumina ceramic film, respectively, and (d) (e) (f) are SEM and cross section of the carbon-coated alumina ceramic film, respectively, and TEM results.
Test example 2
1. Pore size distribution
The ceramic membranes of example 3 and comparative example 1 were tested for pore size distribution by mercury intrusion porosimetry
2. An experimental instrument: U.S. macripheck AutoPore IV 9510 mercury intrusion instrument;
3. the experimental results are as follows:
as can be seen from Table 1 and FIG. 2, the pore diameters corresponding to more than 1% of the pore diameter distribution of the alumina ceramic membrane are concentrated in the range of 40nm to 280nm, and the pore diameters corresponding to 1% of the pore diameter distribution of the carbon-coated alumina ceramic membrane prepared by the method are concentrated in the range of 32nm to 150nm, which indicates that the pore diameter uniformity of the carbon-coated alumina ceramic membrane is significantly improved.
Table 1 pore size distribution of ceramic membranes and carbon-coated alumina ceramic membranes;
test example 3
1. Acid resistance test
The alumina ceramic membrane of comparative example 1 and the carbon-coated alumina ceramic membrane of example 3 were subjected to an acid resistance test, and the ceramic membranes were subjected to a soaking treatment for 24 hours with dilute hydrochloric acid and dilute acetic acid aqueous solutions as acid resistance test solutions, each having a pH of 3.77, and the mass before and after the acid solution treatment was recorded, and the change in acid resistance was judged as the mass loss rate.
2. Experimental reagent: hydrochloric acid (analytically pure, shanghai Lingfeng Chemicals Co., ltd.), acetic acid (analytically pure, shanghai Lingfeng Chemicals Co., ltd.);
3. an experimental instrument: a Sartorius PB-10 ion acidometer, sartorius BSA224S-CW ten thousandth scale;
4. the experimental results are as follows:
as can be seen from table 2 and fig. 3, the alumina ceramic membrane had a significant mass loss after acid treatment for 24 hours in both dilute hydrochloric acid and dilute vinegar, while the mass loss of the carbon-coated alumina ceramic membrane after acid treatment was significantly reduced.
Table 2 mass loss of alumina ceramic films and carbon-coated alumina ceramic films;
from the results of the above test examples, it was found that the carbon-coated alumina ceramic film is improved in the uniformity of pore diameter and the acid resistance, and is more suitable for the treatment of an acidic solution. .
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A ceramic membrane comprising a metal oxide particle-deposited ceramic membrane body, wherein an acid-resistant carbon layer is attached to the surface of the metal oxide particles, and carbon spheres for adjusting the gap are present in the gaps between the metal oxide particles.
2. The ceramic membrane of claim 1, wherein: the metal oxide particles are alumina, zirconia, titania or other metal oxides suitable for preparing metal ceramic membranes.
3. A ceramic membrane according to claim 1, wherein: the carbon layer is an encapsulated carbon layer formed on the surface of the metal oxide particle after the sugar substance is carbonized.
4. A method of preparing a ceramic membrane according to claim 1, wherein: and (3) placing the metal oxide particle accumulation type ceramic membrane main body in a sugar solution for 3 to 12 hours, fully soaking, and carrying out hydrothermal reaction on the soaked ceramic membrane main body to obtain the carbon-coated ceramic membrane.
5. A method for producing a ceramic membrane according to claim 4, wherein: the sugar solution is a sugar water solution, and the concentration of the sugar solution is not lower than 36g/L.
6. A method for producing a ceramic membrane according to claim 4 or 5, wherein: the sugar is monosaccharide, disaccharide, polysaccharide or other saccharides capable of hydrothermal reaction to carbon.
7. A method for the preparation of a ceramic membrane according to claim 4 or 5, wherein: the hydrothermal reaction time is not less than 4 hours, and the reaction temperature is not lower than 120 ℃; or the reaction node of the hydrothermal reaction is as follows: and (3) changing the ceramic membrane from white to brown or brown-like, and stopping the reaction to obtain the carbon-coated ceramic membrane.
8. A method for producing a ceramic membrane according to claim 4, wherein: the ceramic membrane is fully soaked in the sugar solution by adopting a soaking or hydraulic manner.
9. The method for producing a ceramic membrane according to claim 4, wherein: the carbon-coated ceramic membrane is of a shell structure, and the shell structure is an encapsulated carbon layer formed on the surface of ceramic membrane matrix particles after carbohydrates in a carbohydrate solution are carbonized.
10. The method for producing a ceramic membrane according to claim 4, wherein: and (3) cleaning the carbon-coated ceramic membrane with water and ethanol until the eluate is colorless, and drying.
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| US5262198A (en) * | 1991-04-08 | 1993-11-16 | Aluminum Company Of America | Method of producing a carbon coated ceramic membrane and associated product |
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| CN114669741A (en) * | 2022-03-10 | 2022-06-28 | 中国科学院生态环境研究中心 | Nitrogen-doped carbon-coated aluminum material and preparation method and application thereof |
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| US5262198A (en) * | 1991-04-08 | 1993-11-16 | Aluminum Company Of America | Method of producing a carbon coated ceramic membrane and associated product |
| CN104722285A (en) * | 2015-03-27 | 2015-06-24 | 南京理工大学 | Bacterial cellulose membrane/porous carbon adsorbent and preparation thereof |
| TW201908002A (en) * | 2017-07-25 | 2019-03-01 | 日商東麗股份有限公司 | Fluid separation membrane |
| WO2019223086A1 (en) * | 2018-05-25 | 2019-11-28 | 哈尔滨工业大学 | Filter membrane modifying method based on metallic oxide particles |
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| CN114669741A (en) * | 2022-03-10 | 2022-06-28 | 中国科学院生态环境研究中心 | Nitrogen-doped carbon-coated aluminum material and preparation method and application thereof |
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